EP0335024B1 - Immobilisierung von Blei und Kadmium in den Rückständen der Abfallverbrennung durch Gebrauch von Kalk und Phosphat - Google Patents
Immobilisierung von Blei und Kadmium in den Rückständen der Abfallverbrennung durch Gebrauch von Kalk und Phosphat Download PDFInfo
- Publication number
- EP0335024B1 EP0335024B1 EP88302909A EP88302909A EP0335024B1 EP 0335024 B1 EP0335024 B1 EP 0335024B1 EP 88302909 A EP88302909 A EP 88302909A EP 88302909 A EP88302909 A EP 88302909A EP 0335024 B1 EP0335024 B1 EP 0335024B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphate
- fly ash
- cadmium
- lead
- ash
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052793 cadmium Inorganic materials 0.000 title claims description 51
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 49
- 239000007787 solid Substances 0.000 title claims description 42
- 229910019142 PO4 Inorganic materials 0.000 title claims description 41
- 239000004571 lime Substances 0.000 title claims description 37
- 239000010452 phosphate Substances 0.000 title claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 36
- 235000008733 Citrus aurantifolia Nutrition 0.000 title claims description 35
- 235000011941 Tilia x europaea Nutrition 0.000 title claims description 35
- 238000002485 combustion reaction Methods 0.000 title description 7
- 239000010881 fly ash Substances 0.000 claims description 71
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 39
- 229910001868 water Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000010882 bottom ash Substances 0.000 claims description 25
- 239000003546 flue gas Substances 0.000 claims description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 23
- 239000002956 ash Substances 0.000 claims description 19
- 239000002910 solid waste Substances 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 231100000820 toxicity test Toxicity 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 230000003100 immobilizing effect Effects 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- -1 alkali metal salts Chemical class 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims 1
- 235000019798 tripotassium phosphate Nutrition 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 description 36
- 235000011007 phosphoric acid Nutrition 0.000 description 30
- 239000000047 product Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000003916 acid precipitation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 description 6
- 235000019800 disodium phosphate Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 210000000707 wrist Anatomy 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HYHJDTAYSGQLFB-UHFFFAOYSA-K [Pb+3].[O-]P([O-])([O-])=O Chemical compound [Pb+3].[O-]P([O-])([O-])=O HYHJDTAYSGQLFB-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004710 electron pair approximation Methods 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/08—Toxic combustion residues, e.g. toxic substances contained in fly ash from waste incineration
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
Definitions
- the environmental hazard of fly ash containing amounts of cadmium and lead greater than the toxic levels specified by the EPA is somewhat diminished by mixing such ash with heavy ash, such that the resulting landfill mixture is within the toxic levels for the cited metals. Nonetheless, it is highly desirable to reduce the amount of cadmium and lead leached from fly ash and other solid waste to an amount below the toxic levels specified by the EPA.
- the invention herein is a solution to this problem. More specifically it is a method of treating dry solid residues, especially fly ash and mixtures containing fly ash, so as to reduce the amounts of cadmium and lead leached from such residues to a level below the toxic level specified by the EPA.
- the invention herein is a method of immobilizing, or insolubilizing, cadmium and lead in solid waste, especially over a wide pH range.
- the method is convenient, quite simple, very efficient, applicable over a wide pH range, and relatively low cost.
- the method is, therefore, commercially extraordinarily attractive as well as being environmentally beneficial.
- our invention retains the powdery (particulate) nature of the ash-containing residues while immobilizing lead and cadmium: the treated residue remains a particulate, non-hardened solid which does not harden to a brick-like consistency and this characteristic serves as a distinguishing feature of our invention.
- the precipitation of heavy metals, including cadmium and lead, at high pH is a well-known analytical technique, and the use of lime as the basic agent is a common procedure.
- solid wastes containing cadmium and lead were treated with 3-15% calcium hydroxide and/or magnesium sulfate, the pH was adjusted to 8-10.5, and the solid coated with asphalt to prevent the leaching of cadmium and lead.
- Chemical Abstracts, 92:185414d The preceding method is a mixture of coagulation-flocculation followed by encapsulation in a hydrophobic, petroleum-based solid.
- Douglas US-A-4,671,882 describes a coagulation-flocculation process for liquid waste streams.
- the process of the present invention is performed on dry solids and does not rely on physical precipitation processes.
- Pichat describes a process to transform strongly acidic liquid wastes containing relatively high metals content, including cadmium, into solid materials by mixing the wastes with coal fly ash, adjusting the pH to about 7, adding a lime-containing substance and a binder, such as Portland cement, with the mixture setting to a petrified mass; US-A-4,375,986.
- coal ash is pozzolanic, i.e., in the presence of lime it agglomerates into a hard, compact, mortar type product.
- Pichat's invention describes a method to treat acidic liquid wastes and uses coal fly ash as an additive. The patentee also recognizes that coal fly ash does not contain sufficient amounts of Pb and Cd to present an environmental concern.
- coal fly ash which due to chemical composition, surface composition and morphology, and size distribution is pozzolanic.
- incinerator fly ash is not pozzolanic and cannot form a stable cement in the absence of ordinary portland cement.
- the invention described here does not require ordinary portland cement and neither requires nor utilizes solidification or agglomeration for its successful application. Methods applicable to agglomeration or fixation of coal fly ashes are simply not readily applicable to incinerator fly ashes.
- a base course for pavement construction can be made from incinerator ash reacted with lime and water prior to compaction; US-A-4,496,267 EP-A-0 034 389, directed toward the agglomeration of coal fly ash into pellets, discloses some phosphorous compounds in the ash and reports the total phosphorous content as P2O5, but as with Schneider-Arnoldi et al. this phosphorous source does not furnish soluble phosphates.
- fly ash is treated with lime, mixed with bottom ash, and the resulting mixture treated with a source or water soluble phosphate.
- lime originates from flue gas scrubber product.
- the figure shows the final pH of the extract in an EPA test of various solid residues from the burning of solid wastes.
- the cross-hatched part represents the sole region where the EPA Toxicity limits for both lead and cadmium are met in the residues.
- Fly ash also frequently is mixed with lime, in part to immobilize (insolubilize) heavy metals found therein, including lead and cadmium.
- flue gas scrubber product is available it is used either as the sole source of lime or as lime make-up for treatment of the fly ash.
- the fly ash-lime/flue gas scrubber product mixture is then admixed with bottom ash for uses as mentioned above.
- the ratio of bottom ash to fly ash varies considerably, as does the ratio of flue gas scrubber product to fly ash and the extent to which the lime is neutralized in flue gas scrubber product, according to the source of refuse, the operational characteristics of the plant, and so forth.
- the resulting mixture containing flue gas scrubber product, fly ash, and bottom ash has an alkalinity which can vary considerably and additionally displays a broadly varying buffering power.
- such mixtures often fail the EPA test for lead and/or cadmium, essentially because cadmium precipitates at a pH greater than about 7.5 but lead, being amphoteric, begins to redissolve at a pH greater than about 12. Consequently, only in those mixtures whose final pH after extraction in the EPA test ( vide infra ) is between about 7.5 ad about 12.0 are lead and cadmium immobilized sufficiently well for the mixture to be within the stated regulatory limits.
- the practical aspects of refuse burning dictate a broad range of flue gas scrubber product-fly ash-bottom ash solid waste mixtures with an accompanying range of alkalinity.
- the regulatory aspects of solid wastes dictate that leaching of lead be limited to less than 5 ppm and leaching of cadmium to be no more than 1 ppm.
- the technical aspects of the aforementioned solid waste mixtures demonstrate an enormous variation in the leaching of lead and cadmium depending upon pH.
- the problem simply stated, is to make the practical, regulatory, and technical aspects compatible. That is, what can be done to immobilize lead and cadmium in the broad range of solid waste mixtures of flue gas scrubber product-fly ash-bottom ash normally produced in refuse burning plants so as to conform to EPA regulations?
- our invention takes a particulate (powdery or granular) dry solid residue arising from the burning of solid waste in a mass burning plant (from which lead and cadmium are leached at levels of more than 5 and 1 ppm, respectively) and treats the residue with lime, especially that arising from a flue gas scrubber product of a mass burning plant, and one or more water soluble phosphates, to obtain a particulate residue which maintains its particulate nature but from which leaching of lead and cadmium is below the stated levels.
- the solids being treated in our invention are residues resulting from the burning of solid wastes, generally in commercial mass burning facilities, and from which cadmium and/or lead are leached at levels in excess of 1 and 5 ppm, resp., as determined by an EPA test. Initially such solids are a free flowing particulate mass, and a virtue of our invention is that after treatment to immobilize lead and cadmium the solids remain a free flowing particulate mass, even after water percolation, and maintain this characteristic.
- the solids treated generally are fly ash, in whole or in part, since lead and cadmium tend to be concentrated in the fly ash.
- the solid residue treated is a mixture of fly ash and bottom ash, usually containing between 2 and 25% by weight of fly ash, even more often between 5 and 20% fly ash.
- the following description of our invention is couched in terms of the fly ash first being treated with lime or a lime source, with this mixture subsequently being combined with bottom ash prior to addition of a water soluble phosphate. This corresponds to the most convenient way of carrying out our invention, but the choice of this particular description is for expository convenience only.
- the fly ash is mixed with lime.
- lime we mean calcium oxide (dry lime), calcium hydroxide (hydrated lime), a lime source or any mixture thereof.
- the flue gas scrubber product may be either the sole source of lime or may be used only in part as the lime source.
- the FGSP typically will contain such materials as calcium sulfate, calcium sulfite, calcium chloride, and calcium carbonate.
- the percentage of calcium hydroxide in the FGSP is itself subject to broad variation, and the amount of FGSP used will depend in part on the amount of calcium hydroxide present.
- lime or FGSP will be added to fly ash in an amount from 1 to 25 parts by weight of lime, based on its calcium hydroxide content, per 5 parts by weight of fly ash.
- the fly ash-lime mixture is then mixed with bottom ash in the normal, commercial practice of this invention.
- the relative amounts of these two components often is expressed as a ratio of bottom ash to fly ash, and normally varies from perhaps 3:1 to 49:1, i.e., the mixture contains from 2 to 25% by weight fly ash, most often being in the rage of 5-20% by weight fly ash.
- the lime-fly ash-bottom ash mixture is then treated with a source of water soluble phosphate to complete the immobilization of lead and cadmium. It is, perhaps, most convenient merely to spray the mixture with the phosphate source and then agitate the mixture to ensure the dispersion of phosphate. However, merely dispersing a good source of water soluble phosphate through the mixture also may be performed, although not necessarily with equivalent results.
- any convenient source of water soluble phosphate may be used in the practice of this invention.
- a water soluble phosphate is meant a phosphate soluble in water at about 20° C at least to the extent of about five weight-volume percent.
- Phosphoric acids including orthophosphoric acid, hypophosphoric acid, metaphosphoric acid and pyrophosphotic acid, can be conveniently used in this invention.
- phosphates include phosphate, monohydrogen phosphate, and dihydrogen phosphate salts, such as trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, lithium phosphate, lithium hydrogen phosphate, and lithium dihydrogen phosphate.
- the salts of the various phosphoric acids may be utilized, and among these the alkali metal salts are most frequently employed.
- the amount of water soluble phosphate source to be added to the solid residue to ensure adequate immobilization of lead and cadmium will depend on such variables as alkalinity of the solid residue, its buffering capability, the amount of lead and cadmium initially present, and so on. It has been found generally that an amount of the water soluble phosphate source equivalent to between 1% and 8% by weight of phosphoric acid, H3PO4, based on total dry solid residue is sufficient.
- the bottom ash-fly ash mixtures used in our studies contained about 0.5 weight percent phosphorous, which is equivalent to 1.1% reported as P2O5. This shows that the phosphorous-containing materials present in the ash residue is not a source of soluble phosphate necessary for immobilization.
- Solid residues exemplifying a broad spectrum of flue gas scrubber product-fly ash-bottom ash compositions were tested for lead and cadmium content using the EPA test as described above.
- the FGSP typically had a calcium hydroxide content between 40% and 60% so each test required the maximum amount of 0.5N acetic acid before reaching a pH of 5.0.
- the final pH after extraction in the EPA Toxicity test is plotted for various compositions in the figure. It was observed that the EPA limits for Pb were met only within the pH range 6.7-12.0, and the EPA limits for Cd were met only at a pH above 7.5. As can be seen from that figure, only a limited number of such compositions afforded a final pH between 7.5 and 12.0, the range within which the EPA test for both lead and cadmium are met.
- Solid residues were prepared using a ratio of bottom ash to fly ash of 19:1. To this was added flue gas scrubber product containing about 57% free calcium hydroxide in different weight ratios. The EP toxicity test was then run on this mixture of FGSP-fly ash-bottom ash as well as one containing 4.25% phosphoric acid. The results are tabulated below.
- the pH of the concentrated solution was 2.88.
- a solution was prepared for use in the acid rain extraction tests by diluting this mixture by a factor of 10; the resulting pH was 3.93.
- This dilute solution which should be representative of a typical acid rain, was used as a replacement for 0.5N acetic acid to test blends of FGSP, fly ash, and bottom ash. Otherwise, the extraction was identical to the EP Toxicity Test.
- Table 3 demonstrate phosphoric acid addition again was quite effective in reducing the levels of lead leached from such a composite.
- Table 3 Acid Rain Table 3 Acid Rain.
- a composite containing a ratio of bottom ash:fly ash of 19:1 with varying ratios of FGSP:fly ash were tested using from 1% to 4.25% phosphoric acid. As can be seen, even 1% phosphoric acid was generally effective in reducing leaching of lead and cadmium to an acceptable level except with a FGSP:fly ash ratio of 1:1.
- a 19:1 bottom ash-fly ash composition was mixed with an equal amount of flue gas scrubber product and treated with various acids and the anions of these acids.
- the data in Table 8 shows unequivocally that phosphate is unique; neither sulfuric nor nitric acids immobilize lead and cadmium, nor do their salts.
- Example 8 The same mixture of fly ash and flue gas scrubber product as described in Example 8 was treated with .6% phosphorous as phosphate from insoluble Ca3(PO4)2 and then subjected to the EPA leach test.
- the leachate had 19 ppm lead, showing that calcium phosphate is ineffective as a phosphate source in the immobilization of lead by our method.
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- Environmental & Geological Engineering (AREA)
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- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
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Claims (13)
- Verfahren zur Immobilisierung von Blei und Cadmium in einem fließ- bzw. rieselfähigen teilchenförmigen trockenen Feststoffrückstand, der nach der Immobilisierungsbehandlung seine fließ- bzw. rieselfähige teilchenförmige Natur beibehält, wobei der trockene Feststoffrückstand Flugasche und Mischungen aus Flugasche mit Boden- bzw. Herdasche umfaßt, die aus der Verbrennung von Feststoffabfällen stammen, wobei der trockene Feststoffrückstand mit wenigstens einem wasserlöslichen Phosphat in Gegenwart von Kalk in Kontakt gebracht wird, wodurch die Auslaugung von Cadmium und Blei auf eine Menge von nicht mehr als 1 ppm Cadmium und 5 ppm Blei verringert wird, bestimmt in einem EPA-Toxizitätstest, der an dem entstandenen trockenen behandelten Rückstand durchgeführt wurde.
- Verfahren nach Anspruch 1, wobei das wasserlösliche Phosphat in einer 1 bis 8 Gew.-% Phosphorsäure äquivalenten Menge vorliegt, bezogen auf den gesamten trockenen Feststoffrückstand.
- Verfahren nach Anspruch 1 oder 2, wobei der Kalk ausgewählt wird aus trockenem Kalk, hydriertem Kalk, einem Produkt aus einer Abgaswaschvorrichtung und Kombinationen hiervon, und er in einer Menge vorliegt, die ausreichend ist, um 1 bis 25 Gewichtsteile Kalziumhydroxyd pro 5 Gewichtsteile Flugasche bereitzustellen.
- Verfahren nach einem der vorherigen Ansprüche, wobei die Feststoffabfälle kommunale Abfälle sind.
- Verfahren nach einem der Ansprüche 1 bis 3, wobei Blei und Cadmium als fließfähiges teilchenförmiges Material in einem fließfähigen teilchenförmigen trockenen festen Rückstandsmaterial aus einer Mischung aus einer Flugasche und einer Bodenasche immobilisiert vorliegen, wobei jede der genannten Aschen aus der Verbrennung von kommunalem Abfall in einer Materialverbrennungsanlage stammt.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei der trockene Feststoffrückstand 2 bis 25 Gew.-% Flugasche enthält.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei der trockene Feststoffrückstand 5 bis 20 Gew.-% Flugasche enthält.
- Verfahren nach Anspruch 1, wobei der trockene Feststoffrückstand im wesentlichen Flugasche ist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei der Kalk das Produkt einer Abgaswaschvorrichtung aus einer Materialverbrennungsanlage ist.
- Verfahren nach einem der vorhergehenden Ansprüche, wobei das wasserlösliche Phosphat ausgewählt wird aus Phosphorsäure, Polyphosphorsäure, Hypophosphorsäure, Metaphosphorsäure und Salzen hiervon.
- Verfahren nach Anspruch 10, wobei die Salze Alkalimetallsalze sind.
- Verfahren nach Anspruch 11, wobei das Salz Trinatriumphosphat, Dinatriumhydrogenphosphat, Natriumdihydrogenphosphat, Trikaliumphosphat, Dikaliumhydrogenphosphat, Kaliumdihydrogenphosphat, Trilithiumphosphat, Dilithiumhydrogenphosphat, Lithiumdihydrogenphosphat oder Mischungen hiervon ist.
- Verfahren nach Anspruch 10, wobei das wasserlösliche Phosphat Phosphorsäure ist.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/935,899 US4737356A (en) | 1985-11-18 | 1986-11-28 | Immobilization of lead and cadmium in solid residues from the combustion of refuse using lime and phosphate |
EP88302909A EP0335024B1 (de) | 1988-03-31 | 1988-03-31 | Immobilisierung von Blei und Kadmium in den Rückständen der Abfallverbrennung durch Gebrauch von Kalk und Phosphat |
DE3851832T DE3851832T2 (de) | 1988-03-31 | 1988-03-31 | Immobilisierung von Blei und Kadmium in den Rückständen der Abfallverbrennung durch Gebrauch von Kalk und Phosphat. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP88302909A EP0335024B1 (de) | 1988-03-31 | 1988-03-31 | Immobilisierung von Blei und Kadmium in den Rückständen der Abfallverbrennung durch Gebrauch von Kalk und Phosphat |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0335024A1 EP0335024A1 (de) | 1989-10-04 |
EP0335024B1 true EP0335024B1 (de) | 1994-10-12 |
Family
ID=8200012
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88302909A Expired - Lifetime EP0335024B1 (de) | 1985-11-18 | 1988-03-31 | Immobilisierung von Blei und Kadmium in den Rückständen der Abfallverbrennung durch Gebrauch von Kalk und Phosphat |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0335024B1 (de) |
DE (1) | DE3851832T2 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5430233A (en) * | 1991-03-22 | 1995-07-04 | Wheelabrator Environmental Systems, Inc. | Immobilization of lead in solid residues from reclaiming metals |
US5220111A (en) * | 1991-09-10 | 1993-06-15 | Air Products And Chemicals, Inc. | Fixation of heavy metals in scrubbed municipal solid waste incinerator ash |
CZ127492A3 (en) * | 1992-04-27 | 1994-01-19 | Masat Jan | Process for treating materials containing heavy metals |
FR2701222B1 (fr) * | 1993-02-09 | 1995-04-28 | Cnim | Procédé de traitement des résidus solides issus de l'incinération des déchets ménagers et/ou industriels et produit solide obtenu par ce procédé. |
EP1239927B1 (de) | 1999-08-20 | 2005-04-27 | Stramproy Development & Licensing B.V. | Verfahren zum immobilisieren von giftigen metallen in festen industriellen abfällen |
FR2817858B1 (fr) * | 2000-12-13 | 2003-02-07 | Solvay | Procede pour l'inertage d'une cendre, pouzzolane artificielle obtenue au moyen dudit procede |
IT1391955B1 (it) * | 2008-08-21 | 2012-02-02 | Perla S R L | Metodo per trattare materiali contaminati da metalli |
AT512693B1 (de) * | 2012-04-13 | 2013-12-15 | Andritz Energy & Environment Gmbh | Verfahren zur Inertisierung von Schwermetallen, Chloriden und anderen Salzbildnern sowie löslichen Feststoffen und metallischen Kontaminationen |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049462A (en) * | 1976-02-12 | 1977-09-20 | Wehran Engineering Corporation | Chemical fixation of desulfurization residues |
US4354876A (en) * | 1980-09-26 | 1982-10-19 | Webster & Assoc. Ltd. | Utilization of dry scrubber waste materials |
US4496267A (en) * | 1982-12-16 | 1985-01-29 | John P. Gnaedinger Research Corporation | Lime or lime:fly ash pretreated pavement construction material and method |
US4671882A (en) * | 1983-08-31 | 1987-06-09 | Deere & Company | Phosphoric acid/lime hazardous waste detoxification treatment process |
US4737356A (en) * | 1985-11-18 | 1988-04-12 | Wheelabrator Environmental Systems Inc. | Immobilization of lead and cadmium in solid residues from the combustion of refuse using lime and phosphate |
-
1988
- 1988-03-31 DE DE3851832T patent/DE3851832T2/de not_active Expired - Fee Related
- 1988-03-31 EP EP88302909A patent/EP0335024B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0335024A1 (de) | 1989-10-04 |
DE3851832D1 (de) | 1994-11-17 |
DE3851832T2 (de) | 1995-02-09 |
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